title: Photophysical and electrochemical properties of meso-substituted thien-2-yl Zn(II) porphyrins.
abstract: The influence of the thiophene ring on the ground and excited state properties of the porphyrin ring is investigated, when substituted at the meso-position. A series of mono-, di-, tri-, and tetra- meso-thien-2-yl porphyrins are studied and discussed with respect to the reference compounds zinc(II)-5,10,15,20-tetra(thien-2'-yl)porphyrin ( 1a) and zinc(II)-5,10,15,20-tetraphenylporphyrin (ZnTPP). The extended conjugated system zinc(II)-5-(5'-(5''-ethynyl-2''-thiophenecarboxaldehyde)thien-2'-yl)-10,15,20-triphenylporphyrin ( 4d) is also studied and shows enhanced charge transfer character due to the presence of the terminal aldehyde accepting group. A detailed analysis of ground and excited state UV-vis absorption, steady-state and time-resolved fluorescence, laser flash photolysis, and electrochemical data all point toward substantial electronic communication between the central Zn(II) porphyrin ring and the meso-thien-2-yl substituents, which is evident from excited state charge transfer character.
authors.affiliation: School of Chemical Sciences, SRC for Solar Energy Conversion, Dublin City University, Dublin 9, Ireland.
authors.forename: Jonathan
authors.initials: J
authors.lastname: Rochford
authors.forename: Stanley
authors.initials: S
authors.lastname: Botchway
authors.forename: John J
authors.initials: JJ
authors.lastname: McGarvey
authors.forename: A Denise
authors.initials: AD
authors.lastname: Rooney
authors.forename: Mary T
authors.initials: MT
authors.lastname: Pryce
mesh_terms: D000042:Absorption; D004563:Electrochemistry; D005453:Fluorescence; D009682:Magnetic Resonance Spectroscopy; D008665:Metalloporphyrins / Q000737:chemistry*; D013056:Spectrophotometry, Ultraviolet; D013997:Time Factors; D015032:Zinc / Q000737:chemistry*
chemical_list: D008665:Metalloporphyrins; D015032:Zinc